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Modification Of The Devonshire Formula For The Thermal Accommodation Coefficient Of Helium On Tungsten, D. Vincent Roach, Robert E. Harris

Chemistry Faculty Research & Creative Works

The thermal accommodation coefficients (a.c.) of 3He and of 4He on clean tungsten were calculated using the Devonshire formula for temperatures between 70 and 600°K using "realistic" Morse potential parameters. The calculated a.c. values for 3He and 4He and the calculated ratios of the 4He to 3He values are compared with experimental data. The agreement is satisfactory if allowance is made for the error in the transition probability calculation used in the Devonshire formula.

Thermochemical Investigations Of The Methanol-Isopropanol System, Elmer Lee Taylor

Masters Theses

"Heats of solution and partial molar excess volumes at infinite dilution were determined for n-butanol, acetone, chloroform, and water in pure methanol, pure isopropanol, and several mixtures of the two at 25.0⁰C. The partial molar excess enthalpies of methanol and isopropanol were also determined and were combined to obtain integral heats of mixing. All heat data were obtained using a calorimeter of the heat-leak design, containing approximately 300 ml of solvent. Sample sizes ranged for 0.1 to 8 ml. Individual heat measurements were reproducible to 0.05 calories and reported values are considered to be accurate to 1% + 0.5 calorie …

Studies In Syntheses Of Non-Isoprenoid Sesquiterpenes, Raojibhai Javerbhai Patel

Masters Theses

The purpose of this study was to find the shortest route to prepare the 1,9-dimethyl decalone system I, a key intermediate in the synthesis of non-isoprenoid sesquiterpenes. The decalone system I was prepared in good yield by dehydrating the hydroxyketone II with 50% H₂SO₄. The dehydration of hydroxyketone II was also affected by heating in the presence of iodine crystals to yield 80% of the decalone system I.

The basic kinds of approaches under investigation were the Diels-Alder reaction and the Robinson annellation. The Diels-Alder reaction between the conjugated diene, 1-acetoxybutadiene (III) and 2,3-dimethylcyclohexenone (IV) under …

The Vapor-Liquid And Liquid-Liquid Phase Equilibria For The Partially Miscible System Methanol-Cyclohexane, Richard A. Christman

Masters Theses

By use of techniques of previous workers for determining liquid-liquid equilibrium and through the use of a circulation still, the complete phase diagram for the partially miscible system, methanol-cyclohexane, was determined. Tile accuracy of earlier liquid-liquid phase data was not improved upon although it was closely approximated. The critical solution temperature was found to be 46.4 degrees C., which is within the range of temperatures reported in earlier measurements.

Activity coefficients of methanol and cyclohexane were calculated from the phase boundaries of the boiling point diagram determined in the present investigation. These activity coefficients were in agreement with the Gibbs-Duhem …

Noble Gases: A Record Of The Early Solar System, E. C. Alexander

Doctoral Dissertations

"Analyses of the noble gases in samples of iron meteorites are presented which indicate the following: 1. The inclusions of iron meteorites contain noble gases with a wide range of isotopic compositions. 2. The noble gas concentration and isotopic anomalies arc often grossly inhomogeneously distributed within a given inclusion and vary from inclusion to inclusion in a meteorite. 3. Silicate inclusions appear to be the most promising samples for I-Xe and Pu-Xe dating. 4. Graphite and troilite in addition to the silicate inclusion contain significant radiogenic ¹²⁹Xe anomalies. 5. The total I-Xe (and in the case of Toluca silicates total …

The Incorporation Of Oxygen-18 Into Oxindole Acid By Cells Of Hygrophorous Conicus, William Green Allen

Masters Theses

"To understand the mechanism of a biological oxidation in which oxygen is incorporated into a substrate, it is necessary to determine the origin of the incorporated oxygen. The objective of this investigation was to determine the origin of the oxygen atom incorporated into indoleacetic acid (IAA) by the IAA oxidase of Hygrophorous conicus through the use of oxygen-18. To determine the source of the oxygen atom incorporated into IAA it is necessary to incubate H. conicus cells with tryptamine or IAA in the presence of ¹⁸O₂ and H₂¹⁶O in one case and ¹⁶O₂ and H₂¹⁸O in another. An examination of …

Michael Reactions Part Iv Syntheses With Carboalkoxycarbenes, Frederick Ralph Carman

Masters Theses

"A preliminary investigation has been made involving syntheses with dicarboalkoxycarbenes for the purpose of developing new heterocyclic and alicyclic synthese employing functionalized carbenes. The ultimate goals were the development of a stereospecific synthesis of trans fused and angularly substituted ring systems suitable for conversion to natural products and the development of useful synthetic paths to the azabullvalene system. Although these ultimate goals were not realized, new and improved syntheses of alkyl substituted anisoles and diazomalonic esters, including the first reported synthesis of di-tert-butyl-diazomalonate were accomplished. The addition of dicarboalkoxycarbenes to di-, tri- and tetra- substituted ethylenes, tropilidene and 7-aza-tropilidenes by …

Complexes Of Phosphine Ligands With The Main Transition Elements, Richard R. Clikeman '69

Honors Projects

It has been long known that ammonia as well as many primary, secondary and tertiary amines, acts as a ligand forming complexes with the main transition elements.

Semiempirical Determination Of The Hydrogen Bond Energy For Water Clusters In The Vapor Phase. I. General Theory And Application To The Dimer, Richard W. Bolandee, James L. Kassner, Joseph T. Zung

Physics Faculty Research & Creative Works

A simple semiempirical method is given for determining the hydrogen bond energy for water clusters in the vapor phase. This method is based on a general statistical-mechanical theory of clustering. The partition function for a system of clusters is used to determine the equilibrium distribution of clusters. In conjunction with available thermodynamic and spectroscopic data, the cluster equilibrium constants can be used to calculate the cluster potential energy and the hydrogen bond energy. Results for the water dimer agree quite well with other reported values obtained either by quantum-mechanical calculations or approximate thermodynamic estimates. A correct temperature dependence of the …

Reactions Of Difunctional Esters With Benzyl 2-Amino-4,6-0- Benzylidene-2-Deoxy-D-Glucopyranosides, Fred Robert Seymour

University of the Pacific Theses and Dissertations

This research is primarily interested in investigating the reactions of benzyl 2-amino-4,6-0-benzylidene-2- deoxy-D-glucopyranoside (I) with various esters. The advantage offered by this sugar is that an alcohol and an amine group are in close proximity, allowing studies of intermolecular vs. intramolecular reactions and observation on anchimeric assistance in intramolecular reactions.

The Preparation And Determination Of Some Of The Properties Of The Dicarboxylic Amino Acid Chelates Of Platinum(Ii) And Palladium(Ii), Gordon Harold Williams

University of the Pacific Theses and Dissertations

It is surprising that no one has considered that coordination might have some effect on the strength of the acid group. It is the intent of this study to fill this gap in the knowledge of amino-acid chemistry.

At about the time this study began on the effect of chelation on the strength of the uncomplexed acid group, the next two higher homologs of these dicarboxylic amino acids became commercially available. It was, therefore, decided that the problem of this research should be expanded to include all four of the acidic amino acids.

The research problem was also defined to …

Palladium Complexes Of Imino Acids, Kurt Alfredo Freund

University of the Pacific Theses and Dissertations

The nature of this study involves the preparation of coordination compounds of palladium (II) and three imino acids, namely pipecolinic acid, pyrrolidine-20Carbozylic acid and azetidine carboxylic acid.

The Preparation Of Coordination Compounds Of Rhodium (Iii) And Glutamic Acid And Substituted Glutamic Acids, Herman William Kalberer

University of the Pacific Theses and Dissertations

The father of coordination chemistry was Alfred Werner (1866- 1919). Werner's theory was largely responsible for the renewed interest in, and rapid growth of, inorganic chemistry around the turn of the century. He postulated that there were two types of valence, primary and secondary, which correspond, in modern terminology, to oxidation state and coordination number. The primary valences must be either negative ions, neutral molecules or, occasionally even, positive ions (11). He also postulated that the secondary valences are directed in space about the central ion, not only in the solid state, but also when the complex is in solution. …

Isotopic Anomalies Of Noble Gases In Natural Gas, Garry A. Bennett

Masters Theses

"This investigation of the abundance and isotopic composition of noble gases in helium-rich gas wells was undertaken in order to obtain new data which might be used to elucidate the origin of isotopic anomalies of noble gases in the atmosphere. Since noble gases are presently leaking to the atmosphere (Damon and Kulp, 1958a; Bieri et al., 1967-) the isotopic composition of the present atmosphere is not static. The direction of change, and ultimately the origin of anomalous noble gases, might therefore be discovered in studying the noble gases presently leaking from the earth. Since the two major noble gas isotopes …

Das Problem Der Mononitrierung Von Durol, S. B. Hanna, E. Hunziker, T. Saito, H. Zollinger

Chemistry Faculty Research & Creative Works

In contrast to many previous investigations, reaction conditions were found under which the nitration of durene (nitrating ratio of 1:1) gives predominantly, and in high yield, mononitrodurene rather than the usually formed dinitrodurene (plus unreacted durene). The method consists in nitrating by nitronium phosphorohexafluoride in nitromethane as solvent in presence of two equivalents of water. With mixed acid (HNO₃ + H₂SO₄) in nitromethane and in acetonitrile durene forms also monoand no dinitrodurene; but under most conditions by‐products are formed. Some of the by‐products were identified. Some preliminary mechanistic results are reported: An addition complex of …

Ua66/7/2 Newsletter, Wku Chemistry

WKU Administration Documents

Newsletter created by and about the WKU Chemistry department.

An X-Ray Diffraction Study By The Powder Method Of Solid Solutions In The System Zno-Cro3-H2O At 25° C, William Alan Livingston

Masters Theses

No abstract provided.

Studies On 4-Hydroxycoumarin Anticoagulants Part I: The Reversible Removal Of Carbon 2 Of 3-Substituted-4-Hydroxycoumarins Part Ii: The Synthesis And Urinary Excretion Rates Of The Enantiomers Of Warfarin-4-14c And Marcumar-2-14c, Lloyd Allen Goding

Chemistry and Chemical Biology ETDs

The hydrolytic removal and subsequent reinsertion of carbon 2 of a series of 3-substituted-4-hydroxycoumarins has been accomplished. The removal of carbon 2 presents an effective synthetic route to o-hydroxyketones with complex side chains. o-Hydroxyketones when condensed with alkyl carbonates gave good yields of 4-hydroxycoumarins. When this was carried out with ethyl carbonate-carbonyl-¹⁴C a radio label was inserted in position 2. It was shown that this decarboxylation-carboxylation cycle did not involve racemization of an optically active α-carbon on a side chain in position 3. This method was used to prepare the enantiomers of Marcumar-2-¹⁴C(3-α-ethyl-benzyl-4-hydroxycoumarin). The enantiomers of …

A Theoretical Model For Gas Separation In A Glow Discharge: Cataphoresis, Fredrick H. Shair, Donald S. Remer

All HMC Faculty Publications and Research

A theoretical model for transient and steady-state cataphoresis is developed starting with the macroscopic equations of continuity. After a brief breakdown period, the impurity ions are assumed to be closely coupled with their neutral counterparts. The basic assumptions in the model are that after breakdown, the level of ionization of the impurity, and the axial electric field remain constant; it is demonstrated that under these conditions a system involving rapid ionization-recombination reactions is equivalent to a system in which no reaction occurs, but in which the "effective'' ion mobility is a product of the true ion mobility and the fraction …

Expectation Values Of Simple Correlated Helium-Atom Wavefunctions, Thomas P. Tsien, Russell T. Pack

Faculty Publications

In this Note we present the results of a calculation of the expectation values of a number of one- and two electron properties of the ground-state helium atom using two very simple correlated wavefunctions.

Biological Studies Of Selected Reaches And Tributaries Of The Colorado River, Nelson Thomas, Federal Water Pollution Control Administration

Publications (WR)

This report fulfills the request of the Colorado River Basin Project, Denver, Colorado, to determine the effects of municipal and industrial wastes on the aquatic life in selected waters of the Colorado River Basin. These studies were conducted with the assistance of personnel from the Colorado River Basin Project.

Applications Of Modified Wittig Reaction To Butatriene Synthesis, John Pearson

Dissertations and Theses

The preparation of allenes by the condensation of an acyl chloride with a phosphonium ylid and subsequent elimination of an acid salt and a phosphonium oxide has been established by Bestmann and Hartung. It was felt that this process could be expanded to include the synthesis of butatrienes. Butatrienes are stabilized by aromatic substituents while aromatic substituents decrease the nucleophilicity and reactivity of the phosphonium ylids to be used in the synthesis of the butatrienes. The ylids employed were carbomethoxyphenylmethylenetriphenyl phosphorane, and a new compound, carbethoxyphenylmethylenetriphenyl phosphorane, both of which failed to form alkylated condensation products. Both ylids were prepared …

Spectrophotometric Studies Of Complex Formation Of Alpha Aminohydroxamic Acids, Jing Shyong Chen

Masters Theses

No abstract provided.

10th Annual Rocky Mountain Spectroscopy Conference

Rocky Mountain Conference on Magnetic Resonance

Program and abstracts from the 10th annual meeting of the Rocky Mountain Spectroscopy Conference, sponsored by the Rocky Mountain Section of the Society for Applied Spectroscopy. Held in Denver, Colorado, August 19-20, 1968.

Perturbation‐Theoretic Approach To Potential‐Energy Curves Of Diatomic Molecules, Robert Parr, Ronald White

Center for Advanced Mineral and Metallurgical Processing (CAMP)

A perturbation theory is developed whereby the diatomic molecular potential energy W(R) as a function of the internuclear distance R is expressed, for R near R_e, as a power series in the parameter λ = 1 − (R_e/R), W(λ) = w₀ + ∑ (w_n − w_n-1)λ^n.

Truncations of this series have the form of finite power series in R⁻¹. The quantities w_n are obtained simply as perturbation energies for a purely kinetic‐energy perturbation at R_e, by setting up the problem in confocal elliptic coordinates, in …

Determination Of Stability Constants At 25c For The Interaction In Aqueous Solution Of Serine With Co (Ii), Ni (Ii), Cd (Ii), Zn (Ii), And Cu (Ii) Ions, Liak Hwe Ma

Theses and Dissertations

Values of thermodynamic stability constants at 25°C for the complexes of serine with the metal ions. Co^2+, Ni^2+, Cd^2+, Zn^2+, and Cu^2+ were obtained from pH titration data. All measurements were made in aqueous solution, and data were obtained at three different ionic strengths for each metal ion studied. It was assumed that the activity of the zwitterion is unity. The effect of metal ion hydrolysis upon the log K values was taken into account for the calculations. For all the metal ions studied, stability constants for MA^+, MA_2, and MA_3^- were reported with the exception of copper (II) which …

A Study Of Reaction Parameters In The Hydrogenation Of Acetic Acid By Rhenium Heptoxide Catalyst, Victor L. Mylroie

Theses and Dissertations

Rhenium oxides as well as other rhenium compounds are known to display a broad spectrum of catalytic activity,^25 being resistant to attack by acids under nonoxidizing conditions, and showing a remarkable ability to resist poisoning which is a serious limiting factor in many commonly used catalysts. Rhenium catalysts are cheaper than the platinum metals with the exception of palladium. One of the most remarkable properties of the rhenium catalyst is the ability to catalyze the hydrogenation of carboxylic acids and amides to the corresponding alcohols and amines respectively. The carboxyl group (-COOH) is notoriously difficult to reduce catalytically and most …

High Pressure, High Temperature Syntheses Of Rare Earth Diantimonides And Th₃P₄ Type Polymorphs Of Rare Earth Sesquisulfides, Normal L. Eatough

Theses and Dissertations

The rare earths form series of compounds which are known for several elements but end abruptly or undergo a change of structure at some member of the series. The diantimonides are one such series. Sb-Sb repulsion becomes stronger as the rare earth size decreases and the previously known series ended at Sm. It was felt that high pressure would overcome the Sb-Sb repulsion and allow bonding to form stable or metastable compounds not possible by ordinary techniques. Synthesis studies were carried out on mixtures of antimony with all the rare earths except Pm and with Sc and Y. The known …

Preparation Of Phenylsulphur Chloride Tetrafluoride, Dennis T. Sauer

All Master's Theses

The reaction of C6H5SF3, CSF and C12 was studied under a variety of conditions. The reaction run in the presence of a trace of water yielded C6H5SO2F and C1C6H4SO2F. The reaction run in stainless steel at 170°C yielded an amber solid believed to be a polymer with the empirical formula C6H3.67SF2. Chlorination of a C6H5SF3-CSF mixture in monel at 220°C yielded a yellow liquid tentatively identified as a mixture of the new species C6H5SF4C1, FC6H4SF4C1 and C1C6H4SF4C1.

The Reaction Of Ethylenediamine With Cobalt (Ii) Perchlorate And Oxygen In Dilute Aqueous Solutions, Robert J. Karmy

All Master's Theses

Cobalt (II) perchlorate was reacted with ethylenediamine and molecular oxygen. Various mole ratios of ethylenediamine to cobalt (II) were oxygenated and studied by photometric, potentiometric, conductometric, magnetic susceptibility, freezing point depression, electron spin resonance and cobalt (II) extraction methods. The fact that the complex was brown in color, diamagnetic, contained ethylenediamine to cobalt to oxygen in a mole ratio of 4:2:1 was confirmed. The complex underwent elation to form a polymeric species with excess base. The complex could not be oxidized to a green paramagnetic complex by reacting it with sodium peroxydisulfate, potassium bromate, bromine or chlorine. Ammonia was added …